Fluoroaliphatic-thio,-sulfinyl, or sulfonyl substituted bicycloaliphatic amic acid amine salts, and compositions and use thereof

ABSTRACT

Fluoroaliphatic-thio,-sulfinyl and -sulfonyl substituted bicycloaliphatic amic acid amine salts of the formula ##STR1## where R f  is perfluoroalkyl, R&#39; is alkylene optionally interrupted by --O--, --S-- or ##STR2## where R a  is hydrogen or alkyl, Y is lower alkylene or --O--, n is 0-2, R 1  and R 2  are independently hydrogen, lower alkyl, hydroxy lower alkyl or together with the nitrogen to which they are attached, represent morpholino, R 3 , R 4  and R 5  are independently hydrogen, lower alkyl, or hydroxy lower alkyl, R 6  is lower alkyl, carboxy lower alkyl, sulfo lower alkyl, hydroxy lower alkyl, benzyl or together with R 5  and the nitrogen to which they are attached represent morpholino, and R is hydrogen or methyl are provided. These salts applied in the form of aqueous solutions, dispersions or emulsions are useful in rendering cellulosic and natural and synthetic polyamide materials oil and water repellent.

This is a divisional of application Ser. No. 503,435 filed on June 13,1983, now U.S. Pat. No. 4,515,640.

BACKGROUND OF THE INVENTION

The instant invention relates to fluoroaliphatic-thio,-sulfinyl, or-sulfonyl substituted bicycloaliphatic amic acid amine salts, and themanufacture and use of such salts in the form of aqueous solutions,emulsions or dispersions in treating cellulosic materials and natural orsynthetic polyamide materials to render the same oil and waterrepellent.

Fluoroaliphatic-thio substituted bicycloaliphatic anhydrides, useful asstarting materials in the manufacture of the instant amic acid aminesalts, are, in part, disclosed in U.S. Pat. No. 4,082,798, thedisclosure of which is incorporated by reference herein.

While the anhydrides, or corresponding diacids of this U.S. patent, whenconverted to simple metal salts show pronounced surfactant activity,they are unsuitable for the formation of stable aqueous solutions,emulsions or dispersions to render cellulosic or polyamide materialshydrophobic and oleophobic. Moreover, the imides, diamides and diestersexemplified in this reference possess, in general, very limited watersolubility and are thus unsuitable for use as aqueous solutions,emulsions or dispersions in accordance with the instant invention.

It is therefore an object of the instant invention to provide theartisan with novel fluoroaliphatic containing bicycloaliphatic amic acidamine salts, and stable aqueous solutions, emulsions or dispersionscontaining the same as well as the use thereof in rendering cellulosicand polyamide materials oil and water repellent.

It is a further object of the present invention to provide the artisanwith efficient fluorochemical containing aqueous solutions, dispersionsand emulsions providing high fluorochemical pick-up properties oncellulosic and polyamide substrates.

It is a further object of the present invention to provide the artisanwith fluorochemical treated cellulosic and polyamide containingmaterials possessing a high degree of oil and repellent properties, anda method of making the same.

It is yet a further object of the instant invention to provide theartisan with process for the preparation of these compounds.

These and other objects of the invention are apparent from the followingdisclosure.

DETAILED DISCLOSURE

One aspect of the instant invention relates to fluoroaliphaticsubstituted bicycloaliphatic amic acid amine salts of the formula##STR3## wherein

R_(f) is straight or branched chain perfluoroalkyl of 4 to 18 carbonatoms or perfluoroalkoxy-perfluoroalkyl of 4 to 18 carbon atoms;

R' is straight or branched chain alkylene of 1 to 12 carbon atoms,alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2to 12 carbon atoms, or alkyleneiminoalkylene of 2 to 12 carbon atomswhere the imino nitrogen atom contains as a third substituent, hydrogenor alkyl of 1 to 6 carbon atoms;

n is 0, 1 or 2;

Y is lower alkylene or --O--;

R₁ and R₂ are independently hydrogen, lower alkyl, hydroxy-lower alkyl,or together with the nitrogen to which they are attached, representmorpholino;

R₃, R₄ and R₅ independently represent hydrogen, lower alkyl, orhydroxy-lower alkyl,

R₆ is lower alkyl, benzyl, lower alkyl substituted by hydroxy, carboxyor sulfo, or together with R₅ and the nitrogen to which they areattached represent morpholino;

R is hydrogen or methyl; and

wherein the R_(f) --R'--S(O)_(n) -- group is in the 5- or 6-position.

Preferably, R_(f) is perfluoroalkyl of 6 to 14 carbon atoms, R' isalkylene of 1 to 6 carbon atoms, n is 0 or 2, Y is methylene orethylene, R₁ is hydrogen or hydroxy-lower alkyl, R₂ is hydroxy-loweralkyl, or R₁ and R₂ taken together are morpholino, R₃, R₄ and R₅ areindependently hydrogen, lower alkyl or hydroxy-lower alkyl, R₆ ishydroxy-lower alkyl or together with R₅ and the nitrogen to which theyare attached represent morpholino; and

R is hydrogen or methyl.

More preferably, R_(f) is 6 to 12 carbon atoms, R' is alkylene of 2 to 4carbon atoms, n is O, Y is methylene, R₁ is hydrogen or hydroxyethyl, R₂is hydroxyethyl, or R₁ and R₂ taken together with the nitrogen to whichthey are attached represent morpholino, R₃ and R₄ are hydrogen, R₅ ishydrogen or hydroxyethyl, R₆ is hydroxyethyl or taken together with R₅and the nitrogen to which they are attached represent morpholino, and Ris hydrogen.

Most preferred are those compounds of the preceding paragraph whereinR₁, R₂, R₅ and R₆ are hydroxyethyl and R₃ and R₄ are hydrogen.

By "lower" in connection with an aliphatic group is meant those groupscontaining up to 6 carbon atoms, preferably up to 4 carbon atoms, mostpreferably 2 or 3 carbon atoms.

Examples of advantageous amine cations include

H₃ N⁺ CH₂ CH₂ OH,

H₂ N⁺ (CH₂ CH₂ OH)₂,

HN⁺ (CH₂ CH₂ OH)₃,

N⁺ (CH₂ CH₂ OH)₄, ##STR4## H₃ N⁺ CH₂ CHOHCHOHCHOHCHOHCH₂ OH, CH₃ N⁺ H₂CH₂ CHOHCHOHCHOHCHOHCH₂ OH

H₂ N⁺ (CH₂ CHOHCH₃)₂,

H₃ N⁺ C(CH₂ OH)₃,

H₃ N⁺ C(CH₃)₂ CH₂ OH,

H₃ N⁺ CH₂ COOH,

HN⁺ (CH₂ COOH)₃,

H₃ N⁺ -CH₂ CH₂ SO₃ H,

and the like.

In the compounds of formula I, the carbonyl groups in the 2- and3-position of the bicycloaliphatic nucleus may be exo,exo; endo,endo; orexo,endo or mixtures thereof. Preferred are those compounds of formula Iwhich are approximately 1:1 mixtures of the exo,exo and endo,endoisomers.

The compounds of formula I may be prepared by various methods.

In one embodiment, the compounds of formula I are prepared by reacting amercaptan of the formula

    R.sub.f --R'--S--H                                         (II)

wherein R_(f) and R' are as above defined, with a bicycloaliphatic amicacid or salt thereof of the formula ##STR5## where Y, R₁, R and R₂ areas above defined, and M⁺ is the cation of formula I, hydrogen, alkalimetal, alkaline earth metal or ammonium cation.

The reaction ratio can vary widely, e.g. from 2:1 to 1:2 moles of II permole of III, in the presence of an inert diluent such as water, or anaprotic solvent, e.g. dimethylformamide, dimethylsulfoxide,tetrahydrofuran, etc., a lower alkanoic acid, such as acetic acid, alower alkanol, such as ethanol or isopropanol, or mixtures thereof, anda catalytic amount of a free radical initiator, at a temperature betweenabout 0° C. to 100° C. Suitable free radical initiator include peroxidessuch as hydrogen peroxide, peracetic acid, benzoyl peroxide, azocatalysts such as 2-t-butylazo-2-cyanopropane.

To obtain those compounds of formula I wherein n is 1 or 2 from thecompounds produced according to this reaction, the product is oxidizedwith one to two moles of oxidizing agent per mole of product at atemperature of about 0° C. to about 100° C. in the presence of asuitable inert diluent. Suitable oxidizing agents include hydrogenperoxide, peracetic acid, perbenzoic acid, alkali metal periodates ormixtures of hydrogen peroxide and an oxidation catalyst, such astungsten oxide (WO₃).

Where the cation M is other than the cation of formula I, the cation canbe exchanged to that of formula I by methods known per se. Thus, whereM⁺ is hydrogen, the product can be neutralized with a stoichiometricamount of amine or quaternary ammonium hydroxide, optionally in thepresence of an inert diluent, such as water, lower alkanol or mixturesthereof at temperatures between about 0° C. to 100° C. Alternatively,appropriate exchange resins may be used, or the product may be acidifiedwith an inorganic acid to the corresponding free amic acid, separatedfrom the inorganic salt, e.g. where M is an alkali metal, alkaline earthmetal or ammonium, and the free amic acid converted to the compound offormula I.

The compounds of formula III are known per se or can easily be perparedby known techniques.

Thus, the compounds of formula III can be prepared by reacting acompound of the formula ##STR6## wherein Y and R are as defined above,with a compound of the formula ##STR7## where R₁, R₂ and M are as abovedefined, in the presence of a polar solvent, such as acetone, or anaprotic solvent, such as dimethyl sulfoxide, dimethylsulfone, ordimethylformamide, at a temperature between about 20° and 100° C., toform the corresponding Diels-Alder adduct of formula III. As the artisancan appreciate, by the selection of the appropriate amic acid of formulaV, the exo,endo or mixtures of endo and exo,exo, etc. isomers can beobtained.

Alternatively, compounds of formula I can be obtained by reacting acompound of the formula ##STR8## where R_(f), R₁, n, R, and Y are asdefined above, with an amine of the formula ##STR9## where R₁ and R₂ areas defined above, at a temperature between about 0° C. to about 100° C.in the presence of an inert diluent, such as water or an aqueous/loweralkanol mixture, and optionally converting the amic acid product to thecompound of formula I by neutralization, either in situ or as asubsequent step, with an amine, which in the hydroxide form, isrepresented by the formula ##STR10## where R₃, R₄, R₅ and R₆ are definedabove, in an inert diluent, such as water or an aqueous/lower alkanolmixture at a temperature between about 0° C. and about 100° C.

Where R₁ and R₂ are hydroxyalkyl, it is understood that byproductesters-amine may form in minor amounts as a by-product.

Where the amido portion of the compound of formula I corresponds to thecationic amine portion of the compound of formula I, the process of thepreceding paragraph may be simplified by reacting two moles of theappropriate amine of formula VII per mole of anhydride of formula VI.

In addition, in the reaction of the anhydride of formula VI with theamine of formula VII, it is preferred to add the former to a solution ofthe latter. This sequence characteristically results in better yields bysupression of potentially competing hydrolysis of the anhydride to theacid by insuring an excess of amine during the course of the reaction.

Many of the compounds of formula VI are known, via U.S. Pat. No.4,082,798, or are easily prepared by techniques known per se.

For example, the anhydrides of formula VI can be prepared by reacting ananhydride of the formula ##STR11## where Y and R are as defined above,with a mercaptan of the formula

    R.sub.f --R'--S--H                                         (II)

where R_(f) and R' are as defined above, in the presence or absence ofan inert diluent, such as an aprotic solvent, e.g. dimethylformamide,dimethylsulfoxide, tetrahydrofuran, or an alkanoic acid, such as aceticacid, or a lower alkanol, such as ethanol or alkanol/water mixtures, anda catalytic amount of a free radical initiator, at a temperature betweenabout 0° C. and 100° C. Suitable free radical initiators include thosementioned above in the addition reaction of the mercaptan of formula IIwith that of formula III.

The resulting compound can be optionally oxidized to form thosecompounds wherein n is 1 or 2 by the reaction of one or two moles ofoxidizing agent per mole of product at a temperature of about 0° C. toabout 100° C. in the presence of an inert diluent, such as thosementioned in the preceding paragraph. Again, suitable oxidizing agentsinclude hydrogen peroxide, peracetic acid, perbenzoic acid, alkali metalperiodates or mixtures of hydrogen peroxide and an oxidation catalyst,such as tungsten oxide.

In the event hydrolysis occurs, e.g. during the course of the additionreaction between the compounds of formula VIII and II or during optionalsubsequent oxidation, such that the product of formula VI is convertedto the corresponding di-acid, the anhydride can be reformed easily bymeeting of the diacid at elevated temperature and/or reduced pressure,e.g. at a temperature of between about 30° C. and 100° C., to remove thewater therefrom. Alternatively, the water may be removed by azeotropicdistillation e.g. with toluene or benzene, to recover the desiredanhydride of formula VI.

The fluoroaliphatic substituted bicycloaliphatic amic acid amine saltsmay be formulated as aqueous concentrates containing 5% to 60% by weightof the amine salt. Such concentrates are ordinarily clear solutions.

The aqueous concentrate is diluted to an application strength such thatthe aqueous mixture contains 0.01% to 2% by weight, more preferablybetween 0.05% and 0.30% by weight of the amine salt, based on the weightof cellulosic or natural or synthetic polyamide substrate.

Suitable cellulosic and natural polyamide substrates for topicalapplication include paper, non-woven fabrics, textiles, paperboard,wood, wood fiber products such as plywood; hair, including wool, hides,leather, and feathers. Synthetic polyamide substrates include nylonfibers and textiles.

For topical application, suitable aqueous mixture contain,advantageously, 0.01% to 5%, preferably 0.02% to 2%, by weight of theamine salts at use dilution based on the weight of aqueous emulsion.Conventional adjuvants such as water repellant assistants,bacteriostats, coloring agents, surface conditioners and the like, maybe included, e.g. in an amount of between about 0.01% and 5% by weightin the aqueous mixture. Also, sizing agents, where the mixture is to beused on cellulosic substrates, may be present in amounts of from 0.01%to 10% by weight.

The sizing agent may be a natural sizing agent such as animal glue,asphalt emulsions, wax emulsions, rosins, starches; a semisyntheticsizing agent such as a fatty acid salt or complex, a fortified rosin.,e.g., tri sodium maleopimaric acid salt, sodium alginate or sodiumcarboxymethylcellulose; or a synthetic sizing agent such as analkylketene dimer, alkylsuccinic anhydrides, polyvinyl alcohol,styrene-maleic anhydride polymers, and the like. Also mixtures thereofmay be used.

Asphalt emulsions include those obtained from natural deposits or fromthe residue of crude petroleum distillation and emulsified in an aqueoussolution with an emulsifier such as sodium rosinate or fatty amine. Waxemulsions include those prepared from paraffin waxes, optionally blendedwith rosin size and emulsified with a suitable emulsifier, such as guargum, gum arabic, stearic acid salts, lignosulfonate salts, alkylaminesalts, and the like. Starches include corn starch, potato starch, wheatstarch, ethylated corn starch, cationic corn strch corn starch acetate,and the like. Fatty acid salts and complexes include, for example,stearic acid salts, e.g., of aluminum and zirconium, and thecorresponding myristic acid, lauric acid, palmitic acid, margaric acidand behenic acid salts and the corresponding chromium complexes of theseacids with chromium salts, including the Werner type complexes of afatty acid, such as stearic or myristic acid with chromium chloride andisopropanol.

Alkylketene dimers include those wherein the alkyl group is between 6 to23 carbon atoms such as the palmitic, stearic, oleic and myristic ketenedimers, as well as those where the alkyl group is unsaturated orbranched chain, and mixtures thereof.

Alkylsuccinic anhydrides include those where the alkyl group is straightor branched chain and may be saturated or unsaturated having betweenabout 6 to 23 carbon atoms, such as the n-hexadecenylsuccinic anhydride,the dodecylsuccinic anhydride, the dodecenylsuccinic anhydride, theisooctadecenylsuccinic anhydride, and the like.

Also alkylcarbamoyl chlorides, such as ditallowamine carbamoyl chloride;gelatins, cationic aqueous polyurethane emulsions, acrylic resins,stearyl amine surfactants, as known in the art, are suitable sizingagents.

Fillers include materials such as kaolin clay, calcium carbonate,magnesium sulfate, sodium chloride, and the like.

Bacteriostats and fungicides are those commonly used in the paper,leather, fur and textile industries and include halogenated phenols,halogenated carbanilides, o-phenylphenol, salicylic acid anilide,2,2'-methylene-bis(4-chlorophenol), tetraaliphatic ammonium bromides orchlorides, hydroxyquinoline and the like.

Coloring agents include titanium dioxide, and other conventionalinorganic pigments, organic pigments, dyes and optical brighteners.

Surface conditioner adjuvants include paper sizing lubricants, such as afatty acid/polyethylene glycol stearate mixture; swelling agents, suchas an amine oxide swelling agent; extenders, such as urea; fillerretention aids, such as colloidal silica and methyl cellulose; and thelike.

Also, as discussed below, an emulsifier may also be optionally presentin an amount of between about 0.001% to 3% by weight in the composition.

Thus, suitable aqueous compositions for topical application contain

(a) 0.01 to 5% by weight of the amine salt;

(b) 0 to 3% by weight emulsifier;

(c) 0 to 5% water repellant assistant, filler, bacteriostat, coloringagent or surface conditioner adjuvant;

(d) 0 to 10% sizing agent, and

(e) the remainder water.

These aqueous compositions are applied to the surface of the cellulosicor natural or synthetic polyamide material by conventional techniques,including padding, spraying, coating, washing, and brushing. Afterapplication, the treated surface is dried, with or without anintermediate washing stage. The resulting surface is thus rendered waterand oil resistant.

For use as an internal sizing agent to obtain oil and water repellency,the dilution of the instant aqueous compositions advantageously containfrom about 0.0005 to 0.2% by weight of the instant amine salts offormula I. The concentrates for dilution may be prepared as aconcentrate containing between 5% and 60% by weight preferably 15 to 45%by weight, of the amine salt of formula I, based on the amount of water.

In order to insure stability of the amine salt in the aqueous medium,the internal sizing compositions are optionally prepared in the presenceof a conventional emulsifier. Suitable emulsifiers include anionic,amphoteric and non-ionic emulsifiers. It is preferred to use non-ionicemulsifiers, such as block copolymers or ethylene oxide and propyleneoxide.

The amount of emulsifier used, will, of course depend upon theemulsification characterisitcs of the amine salt chosen, as well as thedesired concentration of the amine salt in the aqueous medium. Whereconcentrated emulsions are desired, having between 10 and 40% by weightof the amine salt, it is convenient to use up to 5% of emulsifier. Inmany cases, little or no emulsifier need be added to obtain a clearstable, aqueous compositions.

Preferably, when present, the emulsifier is present in the emulsionconcentrate in an amount between 0.01 and about 3% by weight.

Suitable emulsifiers for use in the present invention includeconventional emulsifiers which are compatible with the active amic acidamine salts of formula I.

Preferred emulsifiers are non-ionic emulsifiers including ethoxylatedlong chain aliphatic amines, ethoxylated long chain aliphatic esters,ethers and thioethers, ethoxylated alkylphenols, block copolymers ofethylene oxide and propylene oxide, and block copolymers of ethyleneoxide and propylene oxide on an alkylene polyamine.

Most preferred nonionic emulisifiers are ethylene oxide/propylene oxideblock copolymers, polyethoxylated octyl and nonyl phenols, and blockcopolymers of ethylene oxide and propylene oxide on ethylene diamine.Suitable nonionic emulsifers are widely commercially available, such asPluronics, including Pluronic F-68, F-87 and F-98 from BASF WyandotteCorp., Tritons, including Triton X-35 and X-114 from Rohm and HaasCorp.; Igepals; including Igepal CO-710 and CO-730 from GAF Corp.; andTetronics, such as Tetronic 904, from BASF Wyandotte Corp.

Pluronics are prepared by condensing ethylene oxide with a hydrophobicbase formed by the condensation of propylene oxide with propylene glycoland may be represented empirically by the formula:

    HO--(C.sub.2 H.sub.4 O).sub.a (C.sub.3 H.sub.6 O).sub.b (C.sub.2 H.sub.4 O).sub.c H.

Pluronic F-68 contains about 80% ethylene oxide units (C₂ H₄ O) and themolecular weight of the polypropylene oxide block (C₃ H₆ O)_(b) is about1,750. Pluronic F-87 contains about 70% ethylene oxide units (C₂ H₄ O)and the molecular weight of the polypropylene oxide block (C₃ H₆ O)_(b)is about 2,250. Pluronic F-98 contains about 80% ethylene oxide units(C₂ H₄ O) and the molecular weight of the polypropylene oxide block (C₃H₆ O)_(b) is about 2,750.

Triton nonionic alkylphenol surfactants are ethoxylated t-octylphenolsor ethoxylated nonylphenols. Triton X-35 is an ethoxylated octylphenolhaving 3 ethylene oxide units and Triton X-114 is likewise anethoxylated octylphenol having 7 to 8 ethylene oxide units, IgepalCO-710 is an ethoxylated nonylphenol having 71% combined ethylene oxideunits by weight of nonylphenol and Igepal CO-730 is an ethoxylatednonylphenol having 73% combined ethylene oxide units by weight ofnonylphenol.

Tetronic 904 is an ethylenediamine/propylene oxide ethylene oxide adductof the approximate formula

    [H(OC.sub.2 H.sub.4).sub.17 (OC.sub.3 H.sub.6).sub.19 ]NCH.sub.2 CH.sub.2 N[(C.sub.3 H.sub.6 O).sub.19 (C.sub.2 H.sub.4 O).sub.17 H].sub.2.

While the instant aqueous emulsions are suitable for rendering a varietyof cellulosic and natural and synthetic polyamide materials oil andwater repellant, the instant emulsions are particularly advantageous inrendering articles made from paper pulp, such as paper trays, paperplates and analogous paper articles, both oleophobic and hydrophobic.

In order to further increase the efficiency of application of theaqueous sizing compositions to the paper pulp, it is desirable topre-treat the paper pulp with a cationic agent, such as cationicallymodified starch, which is adsorbed by the paper pulp and, consequently,tends to increase the amount of fluorochemical transferred from theaqueous emulsion to the cellulose substrate.

Suitable cationic agents, conventionally used to pretreat cellulosematerials such as paper pulp, include conventional cationic modifiedstarches, such as Interbond C, Lok-Size 30, Cato 2, Cato 15 and Cato 17;cationic modified aminoplast resins such as Kymene 557 from HerculesInc.; cationic polymers such as Santo-Res 21 from Monsanto or Reten-210from Hercules Inc.; and cationic blocked polyurethanes such as HypolWB-4000 from W.R. Grace Inc.

Cationic starches are prepared by reacting the starch with amines orquaternary ammonium compounds. Thus, amino ethers of starch are producedby reacting starch with a dialkylaminoalkyl halide which has the aminogroup in the beta-position, as disclosed, for example, in U.S. Pat. No.2,970,140 and Canadian Pat. No. 699,812, both of which describe usefulcationic starches. Further useful cationic starches are described inU.S. Pat. Nos. 2,876,217 and 3,346,563.

Jointly with the fluoroaliphatic substituted bicycloaliphatic amic aminesalts of the invention, can be added one or more of wide choice of waterproofing sizing agents selected from classes such as alkyl anhydrides,e.g. Fibron 68; alkyl ketene dimers e.g. Aquapel 360 XC or Hercon 40:polyurethane emulsions, e.g. Graphsize C; acrylic resins, e.g. Carboset;stearyl amine surfactants, e.g., Ethomeen 18/25 complexed with a fattyacid, e.g. stearic acid; Neofat 14, Neofat 47b or Hystrene 9718.

The amount of adjuvant and sizing agent used for treating paper pulp isof the range specified for topical application, supra.

Thus, for internal sizing of paper pulp suitable aqueous compositionscontain

(a) 0.005 to 0.1% by weight of the instant amine salts;

(b) 0 to 0.05% by weight emulsifier;

(c) 0 to 5% by weight filler, bacteriostat, fungicide, coloring agent orsurface conditioner adjuvant;

(d) 0 to 10% sizing agent; and

(e) the remainder water.

The following examples are intended for illustrative purposes only, andare not intended to restrict the scope of the invention in any way. Allparts are by weight unless otherwise specified.

EXAMPLE 1exo-5-(1,1,2,2-tetrahydroperfluorodecylthio)-bicyclo(2,2,2)octane-endo,endo-2,3-dicarboxylic acid anhydride (Table I, F)

In a 100 ml round bottom flask fitted with a nitrogen inlet tube, areflux condenser, a dropping funnel, and stirred by magnet bar wasplaced endo-bicyclo(2,2,2)octene-2,3-dicarboxylic acid anhydride (4.0 g,0.0224 mole), 1,1,2,2-tetrahydroperfluorodecanethiol (10.8 g, 0.0224mole) and methyl cellosolve acetate (20 g). The solution was heatedunder a nitrogen atmosphere to 80° C. And 2-tert-butylazo-2-cyanopropane(0.2 g) was dissolved in methyl cellosolve acetate (10.0 g) and thesolution was added slowly. This catalyst charge was repeated six timesover a three day period. The reaction was terminated at 37% completion(by G.C.) and the mixture was subjected to steam distillation for 3hours. A crystal slurry in water was formed. The solid material wascollected on a Buchner funnel, dried, and subjected to sublimation(90°-100° C., 0.4 torr, 24 hours). The residue was pure product (4.5 g)m.p. 124°-126° C.

Analysis calc. for C₁₀ H₁₅ F₁₇ SO₃ : 36.3%C, 2.3%H, 48.8%F, 5.4%S.Found: 36.6%C, 2.15%H, 48.4%F, 5.4%S.

EXAMPLE 2exo-5-(1,1,2,2-Tetrahydroperfluorodecylsulfonyl)-2,3-methylnorbornanedicarboxylic acid anhydride [endo,endo/exo,exo isomer mixture (approx.1:1)] (Table I, G)

Exo-5-(1,1,2,2-tetrahydroperfluorodecylsulfonyl)-2,3-methylnorbornanedicarboxylic acid (isomer mixture) (20.0 g, 0.0282 mole) was heated in adraft oven (150° C., 15 hours). The product was dissolved in hot tolueneand treated with activated carbon. After filtration most of the solventwas stripped off. The residue was cooled and the crystalline productcollected (17.0 g, 85% yield).

Anal. Calcd. for C₂₀ H₁₅ F₁₇ O₅ S: 46.78%F. Found: 46.5% FIR(perchloroethylene): 1855 (strong) and 1773 cm⁻¹. (very strong) (>C=o.anhydride).

                                      TABLE I                                     __________________________________________________________________________    Perfluoroalkylthio Group Containing Dicarboxylic Acid Anhydrides              Desig-                                                                        nation                                                                        for                                                                           subse-                                                                        quent                  Configuration                                          exam-                  of anhydride                                                                         R.sub.f -distribution (%)                       ples                                                                              Structure          function                                                                             C.sub.4 F.sub.9C.sub.6 F.sub.13                                                        C.sub.8 F.sub.17C.sub.10 F.sub.21                                                      C.sub.12 F.sub.25C.sub.14                                                     F.sub.29  >C.sub.16                                                                     F.sub.33            __________________________________________________________________________    A.sub.1                                                                            ##STR12##         endo   495      1--      ----      --                  A.sub.2                                                                           "                  "      331      651      ----      --                  A.sub.3                                                                           "                  "      --4      933      ----      --                  A.sub.4                                                                           "                  "      --4      96--     ----      --                  A.sub.5                                                                           "                  "      ----     100 --   ----      --                  A.sub.6                                                                           "                  "      239      3414     83        --                  A.sub.7                                                                           "                  "      12       1657     1 g4      1                   A.sub.8                                                                           "                  "      --3      1025     3518      9                   B.sub.1                                                                           "                  blend of endo                                                                        495      1--      ----      --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.2                                                                           "                  blend of endo                                                                        331      651      ----      --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.3                                                                           "                  blend of endo                                                                        --4      933      ----      --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.4                                                                           "                  blend of endo                                                                        --4      96--     ----      --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.5                                                                           "                  blend of endo                                                                        ----     100--    ----      --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.6                                                                           "                  blend of endo                                                                        239      3414     83        --                                         and exo prod.                                                                 (approx. 1:1)                                          B.sub.7                                                                           "                  blend of endo                                                                        12       1657     194       1                                          and exo prod.                                                                 (approx. 1:1)                                          B.sub.8                                                                           "                  blend of endo                                                                        140      3217     72        1                                          and exo prod.                                                                 (approx. 1:1)                                          B.sub.9                                                                           "                  blend of endo                                                                        --3      1025     3518      9                                          and exo prod.                                                                 (approx. 1:1)                                               ##STR13##         exo                                                    D*                                                                                 ##STR14##         endo                                                   E                                                                                  ##STR15##         blend of endo and exo prod. (approx. 1:1)              F                                                                                  ##STR16##         endo                                                   G                                                                                  ##STR17##         blend of endo and exo prod. (approx.                   __________________________________________________________________________                           1:1)                                                    *n = 6 (70%), n = 8 (30%)                                                

EXAMPLES 3-11

This group of examples illustrates a number of the amines which areuseful for the preparation of mono amide mono salts of this invention.

Five gram portions of the fluoro chemical diacid anhydride A₄ in Table Iwere added to a solution of the amines (listed in Table II) in 25 ml ofwater. The mixture was stirred vigorously and heated to 80° C. (15min.). After cooling samples were taken and characterized by IRspectroscopy after evaporating of most of the water.

The product in example 5 was isolated by evaporating the water in adraft oven and then under vacuum (0.1 torr) over phosphoric pentoxide.In almost quantitative yield a glassy product was obtained.

Analysis Calcd. for C₂₇ H₃₅ F₁₇ N₂ O₇ S: 37.95%C, 4.13%H, 3.28%N,37.79%F, 3.75%S. Found: 37.9%C, 4.1%H, 3.5%N, 37.7%F, 4.0%S.

                                      TABLE II                                    __________________________________________________________________________                            mole ratio                                                              grams of                                                                            R.sub.f -anhydride                                    Example                                                                            Amine        amine used                                                                          amine  IR-analysis                                    __________________________________________________________________________    Examples                                                                      3-13                                                                          3    Monoethanolamine                                                                           0.97  1:2.05 amide I (1680 cm.sup.-1, very strong)               H.sub.2 NCH.sub.2 CH.sub.2 OH                                                                           amide II, salt (1570 cm.sup.-1, strong)                                       ester (1760 cm.sup.-1, very weak)              4    Diethanolamine                                                                             1.67  1:2.0  amide I (1620 cm.sup.-1, strong)                    HN(CH.sub.2 CH.sub.2 OH).sub.2                                                                          salt (1565 cm.sup.-1, strong)                  Examples                                                                      1-11                                                                          5    AMP (IMC)    1.42  1:2.05 amide I (1620 cm.sup.-1, weak)                       ##STR18##                amide II, salt (1540 cm.sup.-1, strong)                                       ester (1740 cm.sup.-1, weak)                   6    Tris         1.92  1:2.05 amide I (1630 cm.sup.-1, shoulder)                  (HOCH.sub.2).sub.3CNH.sub.2                                                                             amide II, salt (1520, 1550 cm.sup.-1,                                         strong)                                                                       ester (1740 cm.sup.-1, strong)                 7    Diisopropylamine                                                                           1.62  1:2.05 amide I (1625 cm.sup.-1, weak)                      HN[CH(CH.sub.3).sub.2 ].sub.2                                                                           salt (1580 cm.sup.-1, strong)                  8    Morpholine   1.38  1:2.05 amide I (1635 cm.sup.-1, very strong)                ##STR19##                salt (1570 cm.sup.-1, strong)                  9    NMethyl taurine                                                                            2.56  1:2.05 amide (1620 cm.sup.-1, strong)                      sodium salt               salt (1565 cm.sup.-1, strong)                       HN(CH.sub.3)CH.sub.2 CH.sub.2 SO.sub.3 Na                                10   Diisopropanolamine                                                                         1.86  1:2.05 amide (1620 cm.sup.-1, strong)                      HN[CH.sub.2 CH(OH)CH.sub.3 ].sub.2                                                                      salt (1565 cm.sup.-1, very strong)                                            salt (1720 cm.sup.-1, weak)                    11   NMethyl glucamine                                                                          3.10  1:2.05 amide (1610 cm.sup.-1, strong)                      HN(CH.sub.3)C.sub.6 H.sub.13 O.sub.5                                                                    salt (1560 cm.sup.-1, strong)                  __________________________________________________________________________

EXAMPLE 12

The mono diethanolamide mono diethanolamine salt ofexo-5-(1,1,2,2-tetrahydroperfluorodecylthio)-endo, endo-2,3-norbornanedicarboxylic acid by aminolysis of the fluorinated norbornanedicarboxylic acid mono methylester was prepared as follows:

Exo-5-(1,1,2,2-Tetrahydroperfluorodecylthio)-endo,endo-2,3-norbornanedicarboxylic acid mono methylester (U.S. Pat. No. 4,082,798) (8.0 g,0.0118 mole) and diethanol amine (16.0 g, 0.152 mol) were combined andheated 90° C. under vacuum for 3 hours. IR shows reaction to be mostlycomplete. IR (film on NaCl): amide I (1620 cm⁻¹, strong), salt (1565cm⁻¹, strong).

EXAMPLE 13

The mono diethanolamide mono diethanolamine salt ofexo-5-(1,1,2,2tetrahydroperfluorodecylthio)-endo,endo-2,3-norbornanedicarboxylic acid by reaction of the nonfluorinated norbornanedicarboxylic acid mono amide mono acid was prepared as follows:

(a) Monomethyl 5-norbornene-endo,endo-2,3-dicarboxylate (50.0 g, 0.25mole) was combined with diethanolamine (60.0 g, 0.55 mole) and heated to140°-145° C. till methanol evolution ceased. Most of the theoreticalyield for methanol was obtained (9.0 ml). The product, a clear amberglass was characterized by IR and used without further purification.

(b) The product obtained in example 13a (50.0 g, 0.124 mole) wasdissolved in water (50 ml). The solution was placed in a 500 ml flaskfitted with stirrer, nitrogen inlet, dropping funnel, and refluxcondenser. Isopropanol (200 ml) and1,1,2,2-tetrahydroperfluorodecanethiol (54.3 g, 0.113 mol) were charged.The mixture was brought to reflux under nitrogen atmosphere and asolution of 2,2'-azobis(2,4-dimethylvaleronitrile in isopropanol (1%, 20g) was added dropwise. After 1 hour all mercaptan was consumed. Excessmercaptan (10 g) was added and the reaction held at reflux for another 2hours. The solvent was evaporated under vacuum and the residue waswashed with methyl ethyl ketone. A gummy solid was obtained and thestructure was confirmed by IR.

EXAMPLES 14-19

These examples demonstrate how the R_(f) -diacid anhydrides can beconverted in mono amid mono carboxylic acid salts and useful emulsionsor solutions simultaneously, in one operation, by weighing aminePluronic F-68 (wetting aid, from BASF Wyandotte), anhydride A₄ (Table I)and water into a 2 ounce jar. The contents were stirred at 70°-80° C.for 10 minutes. Amounts see Table III.

                                      TABLE III                                   __________________________________________________________________________    Examples 14-19                                                                Aqueous Formulations of                                                        ##STR20##                                                                                       weight                                                                            weight of                                                                              calculated     pH of a                             made from 4 g A.sub.4 (Table I)                                                             of dist.                                                                          10%, solution                                                                          solids         1% dilution                    Example                                                                            and the following amine                                                                     water                                                                             of Pluronic F-68                                                                       content                                                                             Appearance                                                                             (w/v) in                       __________________________________________________________________________                                                   water                          14   1.31 g diethanol amine                                                                      16.4 g                                                                            4.40 g   22.0% nearly clear, low                                                                      9.15                                (example 5)                      viscous liquid                          15   1.92 g AMP    15.70 g                                                                           4.40 g   22.0% milky white, free                                                                      8.7                                 example (5)                      flowing liquid                          16   1.08 g Morpholine                                                                           15.61 g                                                                           4.40 g   22.0% clear, low viscous                                                                     8.7                                 (example 8)                      liquid                                  17   1.60 g Diisopropanolamine                                                                   17.46 g                                                                           4.40 g   22.0% light hazy, viscous                                                                    8.7                                 (example 10)                     liquid                                  18   3.36 g NMethyltaurine                                                                       18.42 g                                                                           4.40 g   22.0% clear, low viscous                                                                     8.85                                sodium salt (example 9)          liquid                                  19   2.67 NMethylglucamine                                                                       21.33 g                                                                           4.40 g   22.0% hazy, low viscous                                                                      9.1                                 (example 11)                     liquid                                  __________________________________________________________________________

EXAMPLES 20-41

The use of a number of other fluorinated anhydrides is described in thisgroup of examples.

Using the methods and techniques described in examples 14-19, theexamples listed in Table IV are prepared.

                                      TABLE IV                                    __________________________________________________________________________    Examples 20-41                                                                     Wgt. of R.sub.f                                                                           Wgt. of                                                                            Wgt. of                 pH of a                              Anhydride,                                                                           Wgt. of                                                                            pluronic                                                                           Diethanol                                                                           Calc.             1% dilution                     Example                                                                            Typ (Table I)                                                                        water                                                                              F-68*                                                                              amine % solids                                                                           Appearance   on water                        __________________________________________________________________________    20   4.00 g A.sub.7                                                                       12.38 g                                                                            4.40 g                                                                             1.69 g                                                                              22.0 cloudy, low viscous liquid                                                                 9.07                            21   4.00 g A.sub.2                                                                       16.786                                                                             4.41 g                                                                             1.56 g                                                                              22.0 milky white, low viscous                                                                   9.00                                                             liquid                                       22   4.00 g A.sub.3                                                                       16.81 g                                                                            4.40 g                                                                             1.42 g                                                                              22.0 clear, low viscous liquid                                                                  9.10                            23   4.00 g A.sub.4                                                                       16.4 g                                                                             4.40 g                                                                             1.31 g                                                                              22.0 milky white, low viscous                                                                   9.15                                                             liquid                                       24   4.00 g A.sub.5                                                                       16.4 g                                                                             4.40 g                                                                             1.31 g                                                                              22.0 clear, slightly viscous                                                                    9.06                                                             liquid                                       25   4.00 g A.sub.6                                                                       16.99 g                                                                            4.40 g                                                                             1.47 g                                                                              22.0 opaque, low viscous liquid                                                                 9.24                            26   4.00 g A.sub.7                                                                       15.22 g                                                                            4.40 g                                                                             1.11 g                                                                              22.0 opaque, low viscous liquid                                                                 9.24                            27   4.00 g A.sub.9                                                                       15.99 g                                                                            4.40 g                                                                             1.17 g                                                                              22.0 opaque, straw colored                                                                      9.0                             28   4.00 g B.sub.1                                                                       18.69 g                                                                            4.40 g                                                                             1.95 g                                                                              22.0 cloudy, sl. yellow, low                                                                    8.7                                                              viscous liquid                               29   4.00 g B.sub.2                                                                       18.10 g                                                                            4.40 g                                                                             1.80 g                                                                              22.0 clear, yellowish low                                                                       9.05                                                             viscous liquid                               30   4.00 g B.sub.3                                                                       16.45 g                                                                            4.40 g                                                                             1.32 g                                                                              22.0 clear, low viscous liquid                                                                  8.89                            31   4.00 g B.sub.4                                                                       16.39 g                                                                            4.40 g                                                                             1.30 g                                                                              22.0 hazy, low viscous liquid                                                                   8.93                            32   4.00 g B.sub.5                                                                       18.87 g                                                                            4.40 g                                                                             2.00 g                                                                              22.0 clear, low viscous liquid                                                                  8.74                            33   4.00 g B.sub.6                                                                       16.53 g                                                                            4.40 g                                                                             1.61 g                                                                              22.8 clear, low viscous liquid                                                                  8.98                            34   4.00 g B.sub.7                                                                       15.72 g                                                                            4.40 g                                                                             1.22 g                                                                              22.3 cloudy, low viscous liquid                                                                 9.01                            35   4.00 g B.sub.8                                                                       16.97 g                                                                            4.40 g                                                                             2.05 g                                                                              23.7 cloudy, light amber, low                                                                   8.9                                                              viscous liquid                               36   4.00 g B.sub.9                                                                       15.99 g                                                                            4.40 g                                                                             1.17 g                                                                              21.9 opaque, straw colored                                                                      8.9                             37   4.00 g C                                                                             17.38 g                                                                            4.40 g                                                                             1.58 g                                                                              22.0 clear, low viscous liquid                                                                  9.1                             38   4.00 g D                                                                             16.21 g                                                                            4.40 g                                                                             1.25 g                                                                              22.0 clear, straw colored                                                                       8.9                             39   4.00 g E                                                                             16.31 g                                                                            4.40 g                                                                             1.28 g                                                                              22.0 clear, low viscous liquid                                                                  8.75                            40   2.00 g F                                                                             8.38 g                                                                             2.20 g                                                                             0.70 g                                                                              22.0 low viscous liquid with                                                                    8.56                                                             precipitation                                41   4.00 g G                                                                             17.13 g                                                                            4.40 g                                                                             1.34 g                                                                              22.0 clear, amber, low viscous                                                                  8.94                                                             liquid                                       __________________________________________________________________________     *As 10% (w/v) solution in water                                          

The following examples illustrate how the compounds and dispersions ofthe previous examples can be used to impart oil and water repellentproperties to a variety of substrates.

Application Examples EXAMPLE 42 OIL KIT for Surface Oil Resistance Tests(TAPPI method UM-557)

An easily made kit of twelve solutions of varying proportions of CastorOil, Toluene, and Heptane is useful in comparing surface oil resistance.

    ______________________________________                                                 Volume        Volume   Volume                                        Kit No.  Castor Oil    Toluene  Heptane                                       ______________________________________                                        1        200            0        0                                            2        180           10       10                                            3        160           20       20                                            4        140           30       30                                            5        120           40       40                                            6        100           50       50                                            7         80           60       60                                            8         60           70       70                                            9         40           80       80                                            10        20           90       90                                            11        0            100      100                                           12        0            90       110                                           ______________________________________                                    

The "kit value" is defined as the highest number solution that willstand on the surface of the plate for 15 seconds in the form cf dropswithout failing. Failure is detected by pronounced darkening caused bypenetration. The darkening of even a small fraction of the area underthe drop is considered failure.

This example demonstrates the utility of these dispersions as internalsizes.

Six grams of dry bleached Kraft pulp were diluted in 289 ml distilledwater and thoroughly dispersed in a blender. To this pulp slurry wasadded 4.7 ml of a 1% dilution (as is) of the dispersion from example 24in distilled water. This was mixed in for 5 minutes, then 6 ml of a 1%aqueous solution of cooked cationic starch was added. This was mixedtogether for an additional 5 minutes. To this, 1.2 ml of a 1.5% (onsolids) dilution of an alkyl ketene dimer emulsion was added as a waterrepellent adjuvant. This was mixed in for another 10 minutes. Theresulting slurry was diluted with an additional 500 ml of dist. waterand mixed again. This mixture was then poured over a 100 mesh wirescreen, with a vacuum applied from below which pulled the water from thepulp mixture to form a sheet on the screen. The wet sheet was removedfrom the screen and dried between another screen and hard surface at apressure of approximately 0.4 lbs/in.² at 110° C. for 11/2 hours. Thepaper formed in this manner, showed a TAPPI method UM-557 oil kit numberof 4.

One ml of hot (110° C.) corn oil placed on the paper remained on thesurface and did not penetrate for 20 minutes. Similarly, 1 ml of hot(80° C.) water containing 0.5% of Triton X-165 wetting agent (from Rohm& Haas) placed on the paper did not penetrate for 20 minutes. Whereas,paper made in the same manner, including the cationic starch and waterrepellant adjuvant but without the fluorochemical dispersion;demonstrated an oil kit number of <1, and held the hot corn oil and hotwater/Triton X-165 solution for less than one minute (began to penetrateas soon as applied).

EXAMPLES 43-46

In these examples the utility of various other mono amid mono carboxylicacid amine salts prepared from different fluorinated anhydrides preparedby the method described in examples 14-19 is demonstrated.

The fluorochemical dispersions were evaluated by the method of example42. They show the performance as listed in Table V.

                                      TABLE V                                     __________________________________________________________________________    Examples 43-46                                                                                         Alkyl                                                               Fluorine                                                                           Cationic                                                                           ketene dimer                                                                         Oil         Hot, 80° C.                               on wgt.                                                                            starch                                                                             adjuvant                                                                             test Hot, 110° C.                                                                  water + 0.5%                      Example                                                                            Fluorochemical                                                                          of paper                                                                           on paper                                                                           in paper                                                                             number                                                                             corn oil                                                                             Triton X-165                      __________________________________________________________________________    43   aqueous formulation                                                                     0.05 1.0% 0.3%   3     10 min.                                                                             >20 min.                               prepared as in                                                                          0.06 1.0% 0.3%   4    >20 min.                                                                             >20 min.                               example 15                                                               44   aqueous formulation                                                                     0.05 1.0% 0.3%   3      2 min.                                                                             >20 min.                               prepared as in                                                                          0.06 1.0% 0.3%   3-4  >20 min.                                                                             >20 min.                               example 17                                                               45   aqueous formulation                                                                     0.05 1.0% 0.3%   4    >20 min.                                                                             >20 min.                               prepared as in                                                                          0.06 1.0% 0.3%   4    >20 min.                                                                             >20 min.                               example 39                                                               46   aqueous formulation                                                                     0.05 1.0% 0.3%   3      2 min.                                                                             >20 min.                               prepared as in                                                                          0.06 1.0% 0.3%   5    >20 min.                                                                             >20 min.                               example 41                                                               __________________________________________________________________________

We claim:
 1. A process for rendering a cellulosic or natural orsynthetic polyamide substrate oil and water repellant comprising(A)contacting said substrate with an oil and water repellant impartingeffective amount of an aqueous emulsion comprising (a) 0.01% to 5% byweight of a fluoroaliphatic substituted bicycloaliphatic amic acid aminesalt of the formula ##STR21## wherein R_(f) is straight or branchedchain perfluoroalkyl of 4 to 18 carbon atoms orperfluoroalkoxy-perfluoroalkyl of 4 to 18 carbon atoms; R' is straightor branched chain alkylene of 1 to 12 carbon atoms, alkylenethioalkyleneof 2 to 12 carbon atoms, alkyleneoxyalkylene of 2 to 12 carbon atoms, oralkyleneiminoalkylene of 2 to 12 carbon atoms where the imino nitrogenatom contains as a third substituent, hydrogen or alkyl of 1 to 6 carbonatoms; n is 0, 1 or 2; Y is lower alkylene or --O--; R₁ and R₂ areindependently hydrogen, lower alkyl, hydroxy-lower alkyl, or togetherwith the nitrogen to which they are attached, represent morpholino; R₃,R₄ and R₅ independently represent hydrogen, lower alkyl, orhydroxy-lower alkyl, R₆ is lower alkyl, benzyl, lower alkyl substitutedby hydroxy, carboxy or sulfo, or together with R₅ and the nitrogen towhich they are attached represent morpholino; R is hydrogen or methyl;and wherein the R_(f) --R'--S(O)_(n) -- group is in the 5- or 6-position(b) 0%-3% by weight emulsifier; (c) 0%-5% by weight filler, waterrepellant assistant, coloring agent, or surface conditioner adjuvant;(d) 0%-10% by weight sizing agent; and (e) the remainder water; and (B)drying the treated substrate.
 2. A process for the internal sizing ofpaper pulp and rendering said pulp oil and water repellant comprising(A)contacting said paper pulp with an internal sizing and oil and waterrepellant imparting effective amount of an aqueous emulsion comprising(a) 0.0005-0.1% by weight of an amine salt of the formula ##STR22##wherein R_(f) is straight or branched chain perfluoroalkyl of 4 to 18carbon atoms or perfluoroalkoxy-perfluoroalkyl of 4 to 18 carbon atoms;R' is straight or branched chain alkylene of 1 to 12 carbon atoms,alkylenethioalkylene of 2 to 12 carbon atoms, alkyleneoxyalkylene of 2to 12 carbon atoms, or alkyleneiminoalkylene of 2 to 12 carbon atomswhere the imino nitrogen atom contains as a third substituent, hydrogenor alkyl of 1 to 6 carbon atoms; n is 0, 1 or 2; Y is lower alkylene or--O--; R₁ and R₂ are independently hydrogen, lower alkyl, hydroxy-loweralkyl, or together with the nitrogen to which they are attached,represent morpholino; R₃, R₄ and R₅ independently represent hydrogen,lower alkyl, or hydroxy-lower alkyl, R₆ is lower alkyl, benzyl, loweralkyl substituted by hydroxy, carboxy or sulfo, or together with R₅ andthe nitrogen to which they are attached represent morpholino; R ishydrogen or methyl; and wherein the R_(f) --R'--S(O)_(n) -- group is inthe 5- or 6-position (b) 0.00001 to 0.05% by weight emulsifier (c) 0 to5% by weight filler, bacteriostal, fungicide, coloring agent or surfaceconditioner adjuvant; (d) 0 to 10% sizing agent; and (e) the remainderwater; to render said pulp oil and water repellant, and (B) subsequentlydrying said contacted pulp.
 3. A process according to claim 2, whereinsaid paper pulp is pretreated with a cationic agent.
 4. A processaccording to claim 2, wherein the cationic agent is a cationicallymodified starch, a cationic modified aminoplast resin, a cationicpolymer or a cationic blocked polyurethane.
 5. A process according toclaim 3, wherein the cationic agent is a cationically modified starch.6. A water and oil repellant cellulosic, or natural o r syntheticpolyamide, substrate produced according to the process of claim
 1. 7. Anoil and water repellant paper pulp article produced according to theprocess of claim
 2. 8. An oil and water repellant paper pulp articleproduced according to the process of claim 4.